Azo dye.



UNITED STATES ATENT Furor...

CONRAD SCHRAUBEERHART SOHLEIOHER, AND HANS THEODOR BUOIIERER,

OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, ASSIGNORS. TO THE BA- DISOHE ANILIN 8t SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION OF GERMANY.

AZO DYE.

SPECIFICATION forming part of Letters Patent No. 716,289, dated December 16, 1902.

Application filed August 28, 1900. $eria1No. 28,352. (Specimens) To all whom it may concern.-

Be it known that we, CONRAD SCHRAUBE, doctor of philosophy, a subject of the King of Prussia, Emperor of Germany,.ERHART 5 SCHLEIOHER, doctor of philosophy, a subject ofthe Duke of SaXe-Meiningen, and HANS THEODOR BUOHERER, doctor of philosophy, a subject of the King of Prussia, Emperor of Germany, all residing at Ludwigshafen-onl0 the- Rhine, in the Kingdom of Bavaria, Ger-.

many,have invented new and useful Im provements in Azo Coloring-Matters, of which the following is a specification.

This invention relatesto the production of new azo coloring-matters which may be regarded assulfurous-acid esters of phenolic bodies and which possess the propertyof being converted into difierent and less-soluble H bodies on treatment with caustic soda or sodium carbonate. This change is accompanied by the formation of a sulfite.

' We have discovered that when an aromatic diamin, such as 1.8 or 1.5 naphthylene-diamin, or a sulfo-acid of the same or metatoluylenediamin is suitably subjected to the action of a sulfite, such as sodium .bisulfite, there is formed a substance which hereinafter we will refer to as the sulfurous acid ester of an amide-phenol body, or, for short, sulfurous- 3o acid ester. The so-resulting product is capable of yielding a diazo compound which when combined with a suitable component yields our new azo coloring matters possessing, among others, the above-named property. If

it be desired to convert these new azo coloring-matters,in substance, into the above-mentioned less-soluble products, this may be effected by the use of sodium carbonate or of sulfuric acid. Copper sulfate, copper-sodium 4o glycerate, ferric chlorid, or potassium bichromate also effect a similar conversion. If this is to be effected on the fiber after it has been dyed with our new coloring-matters, it is recommended to use cupric acetate.

In the following examples we illustrate the nature of our invention, but do not wish to be understood as limiting it to these. The parts are. by weight.

Emample 1-Pr0duct1lon of sulfuro-us acid twenty (120) parts of a solution of sodium biester ofan amide-phenol body.One hundred (100) parts of a twenty (20) per cent. solution of the sodium salt of 1.8-naphthylene-diamin-5-sulfo-acid are heated in a vessel provided with a stirrer, with one hundred and sulfite of forty (40) degrees Baum, to a temperature of from ninety to ninety-five degrees. centigrade until a test portion on weak acidulation with hydrochloric acid no longer yields a precipitate of the difficultlysoluble naphthylene-diamin-sulfo-acid. This is usually accomplished in the course of a few hours. The result is introduced into a slight excess of hydrochloric acid of about twenty (20) per cent. strength, and the sulfurous acid is removed by heating.

The so produced sulfurous acid ester of 1.8-amido-naphthol-5-sulfo-acid is soluble in water, giving a yellow-brown solution. It is quite stable toward cold dilute hydrochloric acid even on boiling. Carbonate of soda or caustic soda decomposes it into sodium sulfite and 1.8-amido-naphthol5-sulfo-acid,which can be recognized by any suitable test.

In place of the 1.8-naphthylene-diamin-5- sulfo-acid of the above example we may employ 1.8 -naphthylenediamin itself (which yields the sulfurous-acid esterof 1.8-amidonaphthol) or 1.5 naphthylene diamin or 1.5-naphthylene-diamin-sulfo-acid or metatoluylene-diamin, &c., and the sulfurous-acid ester of an amido-pheno'l body is obtained,and all of these esters have in common the characteristic property that when heated with carbonate of sodium or caustic soda they are decomposed into sodium sulfite and an amidophenol body.

Example 2-Pr0ductt0n of the (haze compound of Ct suZfurous-act'd ester of an amidephenol body.An amount of the sulfurousacid ester which can be obtained from LS-naphthylene-diamin equivalent to six and ninetenths (6.9) parts of sodium nitrite (NaNO is dissolved in five hundred (500) parts of water,and this solution is cooled with ice. To the cooled solution add twenty-five parts of hydrochloric acid, (containing thirty-two (32) per cent. of H01.) Now add seven and one-tenth (7 .1) parts of sodium nitrite,(carrying ninety-eight (98) per cent. of NaNO It is recommended to keep the temperature of the liquid at or about five (5) degrees centigrade. By employing equivalent quantities of other sulfurous-acid esters of an amidophenol body, such as can be obtained from 1.S-naphthylene-diamin-fi-sulfo-acid,1.5-naphthylene diamin, 1.5 naphthylene diaminsulfo-acid, or meta-toluylene-diamin, &c., in place of the sulfurous-acid ester used in this example corresponding diazo compounds can be obtained, and they are all capable of uniting with azo coloringmatter components, forming coloring-matters;

Escample 3-Producti0n of amono-azo coloring-matter containing an unsnlfonated component-The diazo solution resulting from Example 2 when employing the sulfurousacid ester resulting from 1.8-naphthylenediamin is introducedinto a solution of thirtythree (33) parts of crystallized sodium acetate,

' fourteen and four-tenths (14.4) parts of betanaphthol, and four (4) parts of caustic soda dry at a temperature of about fifty (50) degrees centigrade. This coloring-matter dyes wool an orange color. Its aqueous solution on I being boiled with an excess of sodium carbonate yields a violet precipitate.

If the diazo compound employed in the preceding example be combined with equivalent quantities of meta-phenylene-diamin, resorcin, or 2.3-dioxy-naphthalene and the like and in accordance with the ordinary rules of the art for carrying out such operations, our new coloring-matter likewise results.

In place of the diazotized sulfurous-acid ester of the amido-phenol body which can be derived from 1.8-naphthylene-diamin which is employed in this example we can employ the analogous diazotized sulfurous-acid esters of amido-phenol bodies which can be derived from other diamins,as hereinbefore described.

The following table presents some of the properties of some of our new coloring-mat- (NaOH) in one thousand (1,000) parts of tors:

The coloring-matter which can be derived from diazotized Aqueous solution ontreatment with sodium sufurous-acid ester of an amide-phenol body carbonate.

Dyes wool.

From And Cold. Boiling.

LB-naphthylene-diamin Beta-naphthol Orange-red Violet precipitate.

Meta; phenylene-di- Brown-orange Brown precipitate.

amm.

Resorcin Orange Changes from brownyellow to violetbrown.

2-3-dioxy-n ap h tha- Brown-red Changes from r e d- Violet precipitate.

lene. brownish yellow to yellow-brown. 1.s-naphthylene-diamin=5-sulfo acid Beta-naphthol Scarlet Clangels igrom scarlet o vio e Metaphenylenedi Brown Changes from brown amin. ish yellow to bordeanx. 1.5 naphthylene-diamin Beta-naphthol Brownish orange..." Scarlet Violet-red precipitate. 1.5-naphthylene-diamin-sulfo-acid... Beta-naphthol Brownish yellow Changes from brownyellow to dark I brown. Meta-toluylene-diamin Beta-naphthol Brownish orange Becqmes d arker in co or.

The coloring-matter which can be obtained from the diazotised sulfurous-acid ester 0btainable from Lo-naphthylene-diamin sulfoacid and beta-naphthol when boiled with a slight excess of sodium-carbonate solution yields a liquid which it subsequently acidulated with acetic acid yields a ponceau color, while if it be acidulated with hydrochloric acid a violet precipitate results.

Ewample 4--P"roduci'ion of a mono-(120 coloring-matter containing a snlfonaied component.The diazo solution resulting from Ex ample 2 when employing the sulfurous-acid ester resulting from 1.8-naphthylene-diamin is introduced while stirring into a solution of twenty-four (2i) parts of 1.8-amido-naphthol-4-sulfo-acid (pure and free from water) and thirty-six (36) parts of calcined sodium carbonate, which is cooled with ice to about five (5) degrees centigrade. When formation of the coloring-matter ceases, precipitate in the cold by means of common salt, filter, wash with salt brine, press, and dry at a temperature of about fifty (50) degrees centigrade. The co1oring-matter so resulting dyes wool a violet-red, and its solution in a slight excess of sodium carbonate has a red color, which becomes blue on boiling. In place of the 1.S-amido-naphthol-4-sulfo-acid we can employ an equivalent quantity of lA-naphthole sulfo-aoid, and the dyestufi so resulting dyes wool a yellowish red, and'when its aqueous solution is boiled with sodium carbonate it becomes reddish violet.

Example 5Productt'on of a primary disazo c0Zoring-mai2fer.-A. Introduce into the diazo solution resulting from Example 2 when employing the sulfurous-acid ester resulting from 1.8-naphthylene-diamin, while stirring, a neutral solution of twenty-six and onetenth (26.1) parts of the sodium salt of 1.S-amido-naphthol-4-sulfo-acid. When no more coloring-matter is formed, add sufficient sodium carbonate to convert the coloring-matter into its sodium salt and enough water to bring it into solution. Now add twenty-five parts of sodium bicarbonate,

and into this introduce, while stirring, the

diazo compound resulting from nine and three-tenths (9.3) parts of anilin, collect the coloring-matter by precipitating in the cold with common salt, filter, wash with weak salt brine, press, and dry at a temperature of about fifty (50) degrees centigrade. This coloring-matter dyes wool a blue-black shade from an acid-bath, which shade on treatment with copper acetate is changed to a red-.

' old mono-azo coloring-matter by combining in acid solution twenty-three and nine-tenths (23.9) parts of 1.8-amido-naphtholt-sulfo-acid with the diazo compound resulting from nine and three-tenths (9.3) parts of anilin. vert it into its sodium salt by means of sodium carbonate and dissolve it in the requisite quantity of Water. To this solution add twenty-five (25) parts of sodium bicar bonate, and into this introduce,while stirring, the diazo solution resultingfrom Example 2 when employing the sulfurous-acid ester resulting from 1.8-naphthylene-diamin. Collect the coloring-matter by precipitating it with com mon saltin the cold, filter, wash with weak salt brine, press, and dry at a temperature 'of about fifty (50) degrees centigrade. This coloring-matter dissolves in water, giving asolution of a somewhat more reddish cast than the isomeric coloring-matter of Example 5, A. If sodium carbonate be added tothe cold aqueous solution, a violet precipitate results which on boilingin itsliquor dissolves, giving a blue solution. This solution on cooling deposits a blue flocculent precipitate and is distingished from the coloringmatter whose production has been above described by becoming grayish on treatment with hydrochloric acid, whereas the latter changes from violet to bluegr'een. This coloring-matter dyes wool a blue-black shade from an acid-bath, which shade on treatment with copper acetate assumes a greenish cast.

If in place of the sulfurous-acid ester emt ployed in the above example there be used the sulfurous-acid ester which can be ob tained from 1.5-n'aphthylenediamin sulfoacid or from 1.S-naphthyIene-diamin-5-sulfo- Con acid,coloring-matters are obtained which also dye Wool in black shades, and if in place of the anilin of the above example alpha-naphthylamin be employed coloring-matters of analogous properties are obtained.

Example 6-Production of a Secondary disaao coloring-inatter.-Diazotize a quantity of the sulfurous-acid ester resulting from 1.8- naphthylene-diamin-5-sulfo-acid corresponding to siX' and nine-tenths (6.9) parts of sodium nitrite (NaNO by means of twelve (12) parts of hydrochloric acid (containing thirty-two (32) per cent. of H01) and seven and one-tenth (7.1) parts of sodium nitrite, (containing ninety-eight (98) per cent. of NaNO Introduce this diazo solution into a solution containing eighteen (18) parts of the hydrochlorid of alpha naphthylamin. Now add sufficient water to effect solution and diazotize the result by means of twelve (12) parts of the above-described hydrochloric acid and seven and one-tenth (7.1) parts of the above-described sodium nitrite. Since the diazotation takes place but slowly at the temperature ordinarily employedfor such operations, it is recommended to heat the solution to about thirty (30) or forty (40) degrees centigrade. The so-prepared diazo solution is introduced into a solution containing twenty-four and six-tenths (2&6) parts of the sodium salt of lA-naphthol-sulfoacid and thirty (30) parts of calcined sodium carbonate. The coloring-matter resulting can be collected by precipitating with common salt, filtering,washing with dilute salt brine, pressing, and drying, as hereinbefore described. It dyes wool violet. Its aqueous solution when boiled with an excess of sodium carbonate becomes blner in color.

If instead of employing the alkaline solution of 1.4-naphthol-sulfo-acid one uses the equivalent quantity of the hydrochlorid of alpha-naphthylamin, a coloring-matter is obtained which it is recommended to keep in paste form. Its aqueous solution when boiled with an excess of sodium carbonate yields a brownviolet precipitate.

From the foregoing examples it will be seen that the new diazo compounds which can be prepared from hereinbefore-described sulfurous-acid esters of ainido-phenol bodies are capable of application in the production of azo coloring-matters and can be used in the production of almost all types of aizo coloring-matters for which mono-diazo bodies may be employed. It will also be observed that the coloring-matters produced with their aid possess that property which is common to phenolic esters of acids-namely,saponification into the corresponding phenol and acid or salts of the same, in this case sulfurous acid or a sulfite by saponifying agents,1such as sodium carbonate or caustic sOda- -and, further, that the phenolic saponification product is a colored body possessing alcolor dif- It dyes wool a reddish black.

ferent from that of the'esterified coloringmatter and possessing a less greater solubility than the same.

Ournew coloring-matters are distinguished from any hitherto known by the following behavior: When placed in cold dilute five (5) per cent. sulfuric acid, they do not emit an odor of sulfurous acid. If, however, they be boiled with an excess of sodium carbonate and the result be acidified with dilute sulfuric acid, sulfurous acid is liberated.

What is claimed is 1. The azo coloring-matter which on treatment in the cold with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodium-carbonate solution yields a liquid which on addition of an excess of dilute sulfuric-acid, gives sulfurous acid. 7

2. The azo coloring-matter which is a sulfurous-acid ester of a phenolic body and which on treatment in the cold with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodiumcarbonate solution yields a liquid which, on addition of an excess of dilute sulfuric acid, gives sulfurous acid.

3. The polya'zo coloring-matter which is a sulfurous-acid ester of a phenolic body and which on treatment in the cold with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodiumcarbonate solution yields a liquid which, on addition of an excess of dilute sulfuric acid, gives sulfurous acid.

4. The disazo coloring-matter which is a sulfurous-acid ester of a phenolic body and which on treatment in the cold with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodiumcarbonate solution yields a liquid which, on addition of an excess of dilute sulfuric acid, gives sulfurous acid.

5. The primary disazo coloring matter which is a sulfurous-acid ester of a phenolic body and which on treatment in the cold with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodium-carbonate solution yields a liquid which, on addition of an excess of dilute sulfuric acid, gives sulfurous acid.

6. The primary disazo coloring matter which on suitable treatment with a reducing agent yields sulfurous-acid ester of 1.8-amidonaphthol, an aromatic amine, and a diamido derivative of 1.8-amido-naphthol-4t-sulfo-acid, and which coloring-matter on treatment, in the cold, with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodium-carbonate solution, yields a liquid which, on addition of an excess of dilute sulfuric acid, gives sulfurous acid.

7. The primary disazo coloring matter which on suitable treatment with a reducing agent yields sulfurous-acid ester of 1.8-amidonaphthol and a diamido derivative of 1.8- amido-naphthol-et-sulfo-acid and anilin, and which coloring-matter on treatment, in the cold, with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodium-carbonate solution, yields a liquid which, on addition of an excess of dilute sulfuric acid, gives sulfurous acid.

8. The primary disazo coloring matter, which can be obtained by combining a diazotized aromatic amine, in acid solution, with 1.8-amidonaphthol--sulfo-acid and then combining this product, in alkaline solution, with diazotized sulfurousacid ester of 1.8- arnido-naphthol and which coloring-matter on treatment in the cold, with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodium-carbonate solution it yields a liquid which, on addition of an excess of dilute sulfuric acid gives sulfurous acid.

9. The primary disazo .coloring matter which can be obtained by combining diazotized anilin, in acid solution, with 1.8-amidonaphthol-et-sulfoacid and then combining this product, in alkaline solution, with diazotized sulfurous-acid ester of 1.8-amido-naphthol and which coloring-matter on treatment, in the cold, with dilute sulfuric acid does not yield sulfurous acid; but, when boiled with an excess of sodiumcarbonate solution it yields a liquid which, on addition of an excess of dilute sulfuric acid gives sulfurous acid; it dissolves in water giving a violet solution, which solution with sodium carbonate yields a flocculent precipitate in the cold and which precipitate, on boiling in its liquor, dissolves giving a blue solution; the coloringmatter dyes wool a black shade which, on

treatment with copper acetate, assumes a greenish cast.

.In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

CONRAD SOHRAUBE. ERHART SOHLEICHER. HANS THEODOR BUOHERER.

Witnesses:

BERNHARD C. HESSE, JAooB ADRIAN. 

